Effect of Mg/Al atom ratio of support on catalytic performance of Co-Mo/MgO-Al_2O_3 catalyst for water gas shift reaction

Co-Mo-based catalysts supported on mixed oxide supports MgO-Al2O3 with different Mg/Al atom ratios for water gas shift reaction were studied by means of TPR, Raman, XPS and ESR. It was found that the octahedral Mo species in oxidized Co-Mo/MgO（x）-Al2O3 catalyst and the contents of Mo^5＋, Mo^4＋, S^2- and S^2-2 species in the functioning catalysts increased with increasing the Mg/Al atom ratio of the support under the studied experimental conditions. This is favorable for the formation of the active Co-Mo-S phase of the catalysts. Catalytic performance testing results showed that the catalysts Co-Mo/MgO-Al2O3 with the Mg/Al atom ratio of the support in the range of 0.475-0.525 exhibited optimal catalytic activity for the reaction.

Water gas shift activity of Co-Mo/MgO-Al_2O_3 catalysts presulfided with ammonium sulfide

Co-Mo/MgO-Al2O3 catalyst was presulfided with ammonium sulfide in aqueous solution and activated with synthesis gas for water gas shift reaction. The assay results indicate that the presulfided Co-Mo/MgO-Al2O3 catalyst exhibits an excellent catalytic activity and stability. XRD and EPR characterization results show that the O-S exchange might occur during the impregnation, leading to the formation of （NH4）2MoS4 （or （NH4）zMoxSy） precursor, which was then thermally decomposed and reduced to MoS2. The higher catalytic performance is attributed to an optimization formation of active Co-Mo sulfides, consisting of well dispersed MoS2 and Co-Mo-S phase due to the redispersion of Co sulfide particles over the edges of newly formed MoS2 crystallites.

Strong metal-support interactions between highly dispersed Cu^(+) species and ceria via mix-MOF pyrolysis toward promoted water-gas shift reaction

The modulation of metal-support interfacial interaction is significant but challenging in the design of high-efficiency and high-stability supported catalysts.Here,we report a synthetic strategy to upgrade Cu-CeO_(2)interfacial interaction by the pyrolysis of mixed metal-organic framework(MOF)structure.The obtained highly dispersed Cu/CeO_(2)-MOF catalyst via this strategy was used to catalyze water-gas shift reaction(WGSR),which exhibited high activity of 40.5μmolCOgcat^(-1).s^(-1)at 300℃and high stability of about 120 h.Based on comprehensive studies of electronic structure,pyrolysis strategy has significant effect on enhancing metal-support interaction and then stabilizing interfacial Cu^(+)species under reaction conditions.Abundant Cu^(+)species and generated oxygen vacancies over Cu/CeO_(2)-MOF catalyst played a key role in CO molecule activation and H2O molecule dissociation,respectively.Both collaborated closely and then promoted WGSR catalytic performance in comparison with traditio nal supported catalysts.This study shall offer a robust approach to harvest highly dispersed catalysts with finely-tuned metal-support interactions for stabilizing the most interfacial active metal species in diverse heterogeneous catalytic reactions.

Potassium-decorated active carbon supported Co-Mo-based catalyst for water-gas shift reaction

The effect of potassium-decoration was studied on the activity of water-gas shift （WGS） reaction over the Co-Mo-based catalysts supported on active carbon （AC）, which was prepared by incipient wetness co-impregnation method. The decoration of potassium on active carbon in advance enhances the activities of the CoMo-K/AC catalysts for WGS reaction. Highest activity （about 92% conversion） was obtained at 250 ？ C for the catalyst with an optimum K 2 O/AC weight ratio in the range from 0.12 to 0.15. The catalysts were characterized by TPR and EPR, and the results show that activated carbon decorated with potassium makes Co-Mo species highly dispersed, and thus easily reduced and sulfurized. XRD results show that an appropriate content of potassium-decoration on active carbon supports may favors the formation of highly dispersed Co 9 S 8 -type structures which are situated on the edge or a site in contact with MoS 2 , K-Mo-O-S, Mo-S-K phase. Those active species are responsible for the high activity of CoMo-K/AC catalysts.

Support effects on the chemical property and catalytic activity of Co-Mo HDS catalyst in sulfur recovery

Effects of carbon nanotubes （CNT） and alumina （γ-Al2O3） supports on the catalytic activities of hydrodesulfurization （HDS） process over Co- Mo catalyst have been studied. XRD results indicated that the main active phases in CNT and γ-Al2O3 supported Co-Mo catalysts are MoO2 and MOO3, respectively. The TPR results reveal that the reduction peak temperatures of the active species on CNT supported Co-Mo catalyst is lower than those on alumina supported Co-Mo catalyst, indicating that the CNT supports favor the reduction of active species. Catalytic evaluation results displayed that the sulfur content in the reaction products on the CNT supported Co-Mo catalyst is lower than that on the alumina supported Co-Mo catalyst if the HDS reaction was carried out at a temperature above 583 K.

Catalytic Reduction of CO2 to CO via Reverse Water Gas Shift Reaction:Recent Advances in the Design of Active and Selective Supported Metal Catalysts

The catalytic conversion of CO2 to CO via a reverse water gas shift(RWGS)reaction followed by well-established synthesis gas conversion technologies may provide a potential approach to convert CO2 to valuable chemicals and fuels.However,this reaction is mildly endothermic and competed by a strongly exothermic CO2 methanation reaction at low temperatures.Therefore,the improvement in the low-temperature activities and selectivity of the RWGS reaction is a key challenge for catalyst designs.We reviewed recent advances in the design strategies of supported metal catalysts for enhancing the activity of CO2 conversion and its selectivity to CO.These strategies include varying support,tuning metal–support interactions,adding reducible transition metal oxide promoters,forming bimetallic alloys,adding alkali metals,and enveloping metal particles.These advances suggest that enhancing CO2 adsorption and facilitating CO desorption are key factors to enhance CO2 conversion and CO selectivity.This short review may provide insights into future RWGS catalyst designs and optimization.

A Novel γ-Alumina Supported Fe-Mo Bimetallic Catalyst for Reverse Water Gas Shift Reaction

In reverse water gas shift （RWGS） reaction COa is converted to CO which in turn can be used to pro- duce beneficial chemicals such as methanol. In the present study, Mo/AlaO3, Fe/AlaO3 and Fe-Mo/Al2O3 catalysts were synthesised using impregnation method. The structures of catalysts were studied using X-ray diffraction （XRD）, Brunauer-Emmett-Teller （BET） method, inductively coupled plasma atomic emission spectrometer （ICP-AES）, temperature programmed reduction （H2-TPR）, CO chemisorption, energy dispersive X-ray （EDX） and scanning electron microscopy （SEM） techniques. Kinetic properties of all catalysts were investigated in a batch re- actor for RWGS reaction. The results indicated that Mo existence in structure of Fe-Mo/AlzO3 catalyst enhances its activity as compared to Fe/AlaO3. This enhancement is probably due to better Fe dispersion and smaller particle size of Fe species. Stability test of Fe-Mo/AlzO3 catalyst was carried out in a fixed bed reactor and a high CO yield for 60 h of time on stream was demonstrated. Fez（MoO4）3 phase was found in the structures of fresh and used catalysts. TPR results also indicate that Fez（MoO4）3 phase has low reducibility, therefore the Fe2（MoO4）3 phase significantly inhibits the reduction of the remaining Fe oxides in the catalyst, resulted in high stability of Fe-Mo/Al2O3 catalyst. Overall, this study introduces Fe-Mo/Al2O3 as a novel catalyst with high CO yield, almost no by-products and fairly stable for RWGS reaction.

Effects of Cerium on Reduction of Non-Chromium Iron Based CO Shift Catalyst

The effects of Ce on reduction of non-chromium iron based CO shift catalyst were studied by XRD, TPR, SEM and XPS. The results show that Ce refines Fe2O3 grains and riches on the surface of catalyst in the process of reduction, which leads to decrease of the initial reductive temperature and increase of the final reductive temperature.

Effect of Addition Sequence during Neutralization and Precipitation on Iron-based Catalysts for High Temperature Shift Reaction

The preparation of the iron-based catalysts promoted by cobalt with a small amount of copper and aluminum for the high temperature shift reaction （HTS） with different sequences of adding catalyst raw materials during neutralization and precipitation was investigated. XRD, BET and particle size distribution （PSD） were used to characterize the prepared catalysts. It was found that the catalyst crystals were all γ-Fe2O3, and the intermediate of the catalyst after aging was Fe3O4. The crystallographic form of the catalyst and its intermediate was not affected by the addition sequence in the neutralization and precipitation process. The results showed that the specific surface area and the particle size of the catalysts depended on the addition sequence to the mother liquor. Cobalt with a small amount of copper and aluminum could increase the specific surface area and decrease the particle size of catalysts.

Boosting the water gas shift reaction on Pt/CeO_(2)-based nanocatalysts by compositional modification: Support doping versus bimetallic alloying

The water gas shift reaction is of vital significance for the generation and transition of energy due to the application in hydrogen production and industries such as ammonia synthesis and fuel cells.The influence of support doping and bimetallic alloying on the catalytic performance of Pt/Ce O_(2)-based nanocatalysts in water gas shift reaction was reported in this work.Various lanthanide ions and 3d transition metals were respectively introduced into the Ce O_(2)support or Pt to form Pt/Ce O_(2):Ln(Ln=La,Nd,Gd,Tb,Yb)and Pt M/Ce O_(2)(M=Fe,Co,Ni)nanocatalysts.The sample of Pt/Ce O_(2):Tb showed the highest activity(TOF at 200℃=0.051 s^(-1))among the Pt/Ce O_(2):Ln and the undoped Pt/Ce O_(2)catalysts.Besides,the sample of Pt Fe/Ce O_(2)exhibited the highest activity(TOF at 200℃=0.12 s^(-1))among Pt M/Ce O_(2)catalysts.The results of the multiple characterizations indicated that the catalytic activity of Pt/Ce O_(2):Ln catalysts was closely correlated with the amount of oxygen vacancies in doped ceria support.However,the different activity of Pt M/Ce O_(2)bimetallic catalysts was owing to the various Pt oxidation states of the bimetals dispersed on ceria.The study of the reaction pathway indicated that both the samples of Pt/Ce O_(2)and Pt/Ce O_(2):Tb catalyzed the reaction through the formate pathway,and the enhanced activity of the latter derived from the increased concentration of oxygen vacancies along with promoted water dissociation.As for the sample of Pt Fe/Ce O_(2),its catalytic mechanism was the carboxyl route with a higher reaction rate due to the moderate valence of Pt along with improved CO activation.

Effects of ZrO_2 Content on Structure and Performance of Cu/CeO_2-ZrO_2 Catalysts for Water-Gas Shift Reaction

Cu/CeO2-ZrO2 catalysts for water-gas shift （WGS） reaction were prepared with co-precipitation method, and the influence of ZrO2 content on the catalytic structure and properties was investigated by the techniques of N2 physical adsorption analysis, XRD and H2-TPR. The results indicate that the BET surface areas of the catalysts are increased in varying degrees due to the presence of ZrO2. With increasing ZrO2 content, the pore size distribution is centered on 1.9 nm. ZrO2 can efficiently restrain the growth of Cu crystal particles. The appropriate amount of ZrO2 in the Cu/CeO2 catalysts can help the catalyst keep better copper dispersion in the WGS reaction, which can lead to both higher catalytic activity and better thermal stability. When ZrO2 content is 10% （atom fraction）, Cu/CeO2-Zr02 catalyst reaches a CO conversion rate of 73.7% at the reaction temperature of 200℃.

Kinetics of the water-gas shift reaction in Fischer-Tropsch synthesis over a nano-structured iron catalyst

Based on formate and direct oxidation mechanisms,three Langmuir-Hinshelwood-Hougen-Watson （LHHW） kinetic models of the water-gasshift （WGS） reaction over a nano-structured iron catalyst under Fischer-Tropsch synthesis （FTS） reaction conditions were derived and compared with those over the conventional catalyst.The conventional and nanostructured Fe/Cu/La/Si catalysts were prepared by co-precipitation of Fe and Cu nitrates in aqueous media and water-oil micro-emulsion,respectively.The WGS kinetic data were measured by experiments over a wide range of reaction conditions and comparisons were also made for various rate equations.WGS rate expressions based on the formate mechanism with the assumption that the formation of formate is rate determining step were found to be the best.

For more and purer hydrogen-the progress and challenges in water gas shift reaction

The water gas shift(WGS) reaction is a standard reaction that is widely used in industrial hydrogen production and removal of carbon monoxide. The improved catalytic performance of WGS reaction also contributes to ammonia synthesis and other reactions. Advanced catalysts have been developed for both high and low-temperature reactions and are widely used in industry. In recent years, supported metal nanoparticle catalysts have been researched due to their high metal utilization. Low-temperature catalysts have shown promising results, including high selectivity, high shift rates, and higher activity potential. Additionally, significant progress has been made in removing trace CO through the redox reaction in electrolytic cell. This paper reviews the development of WGS reaction catalysts, including the reaction mechanism, catalyst design, and innovative research methods. The catalyst plays a crucial role in the WGS reaction, and this paper provides an instant of catalyst design under different conditions. The progress of catalysts is closely related to the development of advanced characterization techniques.Furthermore, modifying the catalyst surface to enhance activity and significantly increase reaction kinetics is a current research direction. This review goals to stimulate a better understanding of catalyst design, performance optimization, and driving mechanisms, leading to further progress in this field.

Effect of yttrium addition on water-gas shift reaction over CuO/CeO_2 catalysts

This paper presented a study on the role of yttrium addition to CuO/CeO2 catalyst for water-gas shift reaction. A single-step co-precipitation method was used for preparation of a series of yttrium doped CuO/CeO2 catalysts with yttrium content in the range of 0-5wt.%. Properties of the obtained samples were characterized and analyzed by X-ray diffraction （XRD）, Raman spectroscopy, H2-TPR, cyclic voltammetry （CV） and the BET method. The results revealed that catalytic activity was increased with the yttrium content at first, but then decreased with the further increase of yttrium content. Herein, CuO/CeO2 catalyst doped with 2wt.% of yttrium showed the highest catalytic activity （CO conversion reaches 93.4% at 250 ℃） and thermal stability for WGS reaction. The catalytic activity was correlated with the surface area, the area of peak γ of H2-TPR profile （i.e., the reduction of surface copper oxide （crystalline forms） interacted with surface oxygen vacancies on ceria）, and the area of peak C2 and A1 （Cu^0→←Cu^2＋ in cyclic voltammetry process）, respectively. Besides, Raman spectra provided evidences for a synergistic Cu-Ovacancy interaction, and it was indicated that doping yttrium may facilitate the formation of oxygen vacancies on ceria.

Influence of Gas Components on the Formation of Carbonyl Sulfide over Water-Gas Shift Catalyst B303Q

Water-gas shift reaction catalyst at lower temperature （200-400 ℃） may improve the conversion of carbon monoxide. But carbonyl sulfide was found to be present over the sulfided cobaltmolybdenum/alumina catalyst for water-gas shift reaction. The influences of temperature, space velocity, and gas components on the formation of carbonyl sulfide over sulfided cobalt-molybdenum/alumina catalyst B303Q at 200-400 ℃ were studied in a tubular fixed-bed quartz-glass reactor under simulated water-gas shift conditions. The experimental results showed that the yield of carbonyl sulfide over B303Q catalyst reached a maximum at 220 ℃ with the increase in temperature, sharply decreased with the increase in space velocity and the content of water vapor, increased with the increase in the content of carbon monoxide and carbon dioxide, and its yield increased and then reached a stable value with the increase in the content of hydrogen and hydrogen sulfide. The formation mechanism of carbonyl sulfide over B303Q catalyst at 200-400 ℃ was discussed on the basis of how these factors influence the formation of COS. The yield of carbonyl sulfide over B303Q catalyst at 200-400 ℃ was the combined result of two reactions, that is, COS was first produced by the reaction of carbon monoxide with hydrogen sulfide, and then the as-produced COS was converted to hydrogen sulfide and carbon dioxide by hydrolysis. The mechanism of COS formation is assumed as follows： sulfur atoms in the Co9Ss-MoS2/Al2O3 crystal lattice were easily removed and formed carbonyl sulfide with CO, and then hydrogen sulfide in the water-gas shift gas reacted with the crystal lattice oxygen atoms in CoO-MoOa/Al2O3 to form Co9S8-MoS2/Al2O3. This mechanism for the formation of COS over water-gas shift catalyst B303Q is in accordance with the Mars-Van Krevelen＇s redox mechanism over metal sulfide.

Promotion effect of Re additive on the bifunctional Ni catalysts for methanation coupling with water gas shift of biogas: Insights from activation energy

The cheap manganese sand was first modified by H2O2 and was further creatively utilized as Ni-based catalyst support.In order to enhance the catalytic performance,Re was added into the Ni-based catalyst and the promotion effect of Re on the methanation coupling with water gas shift of biogas was investigated from the perspective of activation energy.It was found that CH4 and CO2 formation rates,which separately represented the reaction rate of methanation and water gas shift,were both enhanced after Re addition compared to non-added catalyst.Two kinetics models including empirical model and K-model were employed and from the results of calculation,it showed that Re selectively decreased the activation energy of methanation reaction and had little impact on the activation energy of water gas shift.The increased CO2 formation rate was owing to the assistance of accelerated H2O production from methanation rather than the activation energy change in water gas shift.

CHARACTERIZATION OF COBALT SITES IN REDUCED Co-Mo/Al_2O_3 AND Ru-Co-Mo/Al_2O_3 CATALYSTS

The two Co sites are well characterized in reduced Co-Mo/Al_2O_3 and Ru-Co- Mo/Al_2O_3 by new bands at 1895 and 1880 cm^(-1)in the IR spectra due to NO adsorption.

Performance and Industrial Application of New-Type Sulfur Tolerant CO Shift Catalyst QDB-04

This paper presents the performance and characteristics of new-type sulfur tolerant shift catalyst QDB-04 and its industrial side-line test as well as the first-time industrial application in Lunan Chemical Fertilizer Plant of Shandong in China. The results show that the catalyst has high strength and strength stability, good low temperature activity and stability as well as low potassium bleeding ratio which well meet for the requirements of the methanol plant on catalyst performance in Lunan Chemical Fertilizer Plant.

以ZrO_2-Al_2O_3为载体Co-Mo-K耐硫变换催化剂的TPR研究

利用程序升温还原 (TPR)技术 ,研究了ZrO2 对Co/Al2 O3、Mo/Al2 O3、Mo -K/Al2 O3以及Co -Mo -K耐硫变换催化剂氧化还原性能的影响。结果表明 ,ZrO2 的引入 ,使活性组分在载体表面分散的更好 ,促进了Mo -K活性相的形成 ,使Co和Mo的还原变得容易 ,并起到抑制催化剂在反应中被重新氧化的作用。

混合法制备Co-Mo/MgO-Al_2O_3变换催化剂的XRD和TPR表征

用混合煅烧法制备的Co Mo/MgO Al2O3一氧化碳变换催化剂,在2.0MPa及多种汽气比条件下与同类型催化剂进行活性评价比较,达到德国催化剂K8 11的活性水平.对催化剂及参比样MoO3/Al2O3、MoO3/MgO Al2O3和MgO Al2O3等进行XRD或TPR表征,结果显示Co Mo/MgO Al2O3催化剂存在MoO3、CoMoO4、MgMoO4和MgAl2O4等物种,单纯的Mo在MgO Al2O3载体上分散度比在γ Al2O3载体上低,MoO3的结晶度较高,其还原温度提高;添加Co后,MoO3的分散度得到提高.在Co Mo/MgO Al2O3催化剂的TPR谱中出现属于MoO3(624℃)和CoMoO4(805℃)的两个还原峰,该催化剂对CO变换活性的提高与CoMoO4相的生成密切相关.